Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM2(M = Rh, Ir) Early−Late Heterobimetallic Complexes

Abstract

Reactions of the zirconium−sulfide metallocene anion [Cptt2ZrS2]2- (Cptt = η5-1,3-di-tert-butylcyclopentadienyl) with [{M(μ-Cl)(diolefin)}2 gave the d0−d8 complexes [Cptt2Zr(μ3-S)2{M(diolefin)}2] (M = Rh, diolefin = 2,5-norbornadiene (nbd) (1), 1,5-cyclooctadiene (cod); M = Ir, diolefin = cod) with a triangular ZrM2 core capped by two symmetrical μ3-sulfido ligands. The rhodium complexes [Cptt2Zr(μ3-S)2{Rh(diolefin)}2] (diolefin = tetrafluorobenzobarrelene (tfbb), nbd, cod) can also be prepared by the additive-deprotonation reactions of the mononuclear [Rh(acac)(diolefin)] (diolefin = nbd, tfbb) and the dinuclear [{Rh(μ-OH)(cod)}2] complexes with [Cptt2Zr(SH)2]. These compounds exist as two rotamers in solution due to a hindered rotation of the cyclopentadienyl rings and the relative disposition of the substituents of the Cptt groups in the sandwich moiety. The reaction of [Cptt2Zr(SH)2] with [Ir(acac)(cod)] gave the complex [Cptt(acac)Zr(μ3-S)2{Ir(cod)}2] (5) with release of HCptt and coordination of acetylacetonate to the zirconium center. Carbonylation of compounds 1 and 5 yielded [Cptt2Zr(μ3-S)2{Rh(CO)2}2] (6) and [Cptt(acac)Zr(μ3-S)2{Ir(CO)2}2], respectively, while the complexes [Cptt2Zr(μ3-S)2{M(CO)2}2] (M = Rh, Ir) resulted also from the reaction of [Cptt2Zr(SH)2] with (PPh3Bz)[MCl2(CO)2] in the presence of triethylamine. Reactions of the carbonyl complexes with 1 molar equiv of bis(diphenylphosphino)methane (dppm) gave the cisoid complexes [Cptt2Zr(μ3-S)2{M(CO)}2(μ-dppm)] (M = Rh (9), Ir) with evolution of carbon monoxide. Monodentate phosphites, P(OMe)3 and P(OPh)3, react with 6 to give mixtures of the transoid and cisoid isomers [Cptt2Zr(μ3-S)2{Rh(CO)(P(OR)3)}2], which also exhibit a restricted rotation of the Cptt rings. The molecular structures of complexes 6 and 9 have been determined by X-ray diffraction methods. Compound 6 in the presence of P-donor ligands, P(OMe)3, P(OPh)3, and PPh3, is a precursor of the catalyst for the hydroformylation of oct-1-ene under mild conditions of pressure and temperature. No Zr−Rh synergic effect is observed in this case, and the precursor breaks down after catalysis.